Branched chain olefinic alcohols, thiols, esters and ethers, organoleptic uses thereof, processes for preparing same and intermediates therefor

ABSTRACT

Described is the novel compound genus defined according to the structure: ##STR1## wherein R 1  is selected from the group consisting of methyl and isopropyl alcohol and wherein the dashed lines represents a carbon-carbon double bond and each of the other of the dashed lines represent carbon-carbon single bonds useful in augmenting or enhancing the aroma or taste of consumable materials including perfumes, colognes, perfumed articles (including solid or liquid anionic, cationic, nonionic or zwitterionic detergents) smoking tobacco or smoking tobacco articles.

This is a divisional of application Ser. No. 252,334, filed Apr. 9,1981, now U.S. Pat. No. 4,336,164, which in turn, is acontinuation-in-part of application for United States Letters Patent,Ser. No. 212,887 filed on Dec. 4, 1980 now U.S. Pat. No. 4,318,934.

BACKGROUND OF THE INVENTION

Materials which can provide amber, woody and fruity aroma profiles withvetiver-like topnotes particularly those materials which are relativelyinexpensive are highly sought after in the art of perfumery. Many of thenatural materials which provide such fragrance profiles and contributedesired nuances to perfumery compositions and perfumed articlesubstances are high in cost, vary in quality from one batch to anotherand/or are generally subject to the usual variations of naturalproducts.

There is, accordingly, a continuing effort to find synthetic materialswhich will replace the essential fragrance notes provided by naturalessential oils or compositions thereof. Unfortunately, many of thesesynthetic materials either have the desired nuances only to a relativelysmall degree or else contribute undesirable or unwanted odor to thecomposition. The search for materials which can provide a more refinedamber, woody, fruity and vetiver-like aroma has been difficult andrelatively costly in the areas of both natural products and syntheticproducts.

Materials which can provide woody, oriental and minty aroma and tasteprofiles both prior to and on smoking in the mainstream and thesidestream of smoking tobacco articles are desirable for augmenting orenhancing the aroma and taste of smoking tobacco and smoking tobaccoarticles, e.g. cigarettes and cigars.

Even more desirable is a product that can serve to substitute fordifficult-to-obtain natural perfumery oils and expensive syntheticingredients of perfume compositions and, at the same time, substitutefor expensive flavoring ingredients in smoking tobacco and in smokingtobacco articles.

Perfumery materials which are inexpensive such as dihydrolinalool(3,7-dimethyl-6-octen-3-ol) and dihydromyrcenol(3-methylene-7-methyloctanol-7) do not provide the vetiver-likefragrance profiles that are provided by the more expensive, more complexmolecules such as vetivone.

Dihydro linalool according to "Perfume and Flavor Chemicals (AromaChemicals)" by Steffen Arctander (1969) having the structure: ##STR2##at Monograph 960 is indicated to have a fresh, floral, citrusy aromawhich is less woody than linalool and more powerful and more lime-likethan tetrahydro linalool. On the other hand, dihydro myrcenol having thestructure: ##STR3## (at number 964 of Arctander) is described as beingpowerful, fresh lime-like overall citrusy, floral and sweet with littleor no terpenic undertones. Dihydro myrcenyl acetate described atMonograph 965 of Arctander having the structure: ##STR4## is describedas sweet, spicy, herbaceous, fresh and somewhat fruity with abergamot-like character but poor tenacity.

The chemicals described in the prior art such as dihydro myrcenylacetate, dihydro myrcenol or dihydro linalool have aroma profiles orchemical structures which are not even remotely similar to the compoundsof our invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. AA represents the GLC profile for the reaction product of Example Ausing a 70% sulfuric acid catalyst at 35% C.

FIG. AB represents the GLC profile for the reaction product of Example Ausing an Amberlyst® 15 acidic ion exchange resin catalyst at atemperature of 150° C.

FIG. AC represents the GLC profile for the reaction product of ExampleA, using an Amberlyst® 15 catalyst at 100° C.

FIG. AD represents the GLC profile for the reaction product of ExampleA, using a sulfuric acid catalyst and an alpha-methylstyrene diluent at35° C. according to the conditions of United Kingdom PatentSpecification No. 796,130 (crude reaction product).

FIG. AE represents the GLC profile for the reaction product of ExampleA, using a sulfuric acid catalyst, at 35° C. and an alpha-methyl styrenediluent according to the conditions of United Kingdom PatentSpecification No. 796,130 (distilled reaction product).

FIG. BA represents the NMR spectrum for Peak 1 of the GLC profile ofFIG. AE.

FIG. BB represents the infra-red spectrum for Peak 1 of the GLC profileof FIG. AE.

FIG. CA represents the NMR spectrum for Peak 2 of the GLC profile ofFIG. AE.

FIG. CB represents the infra-red spectrum for Peak 2 of the GLC profileof FIG. AE.

FIG. D represents the NMR spectrum for Peak 2 of the GLC profile of FIG.AB.

FIG. 1 sets forth the GLC profile for the reaction product of Example I,containing compounds defined according to the structure: ##STR5##wherein in each molecule of the mixture, one of the dashed lines is acarbon-carbon double bond and the other of the dashed lines arecarbon-carbon single bonds.

FIG. 2A represents the infra-red spectrum for Peak 3 of the GLC profileof FIG. 1.

FIG. 2B represents the infra-red spectrum of Peak 4 of the GLC profileof FIG. 1.

FIG. 2C represents the infra-red spectrum for Peak 5 of the GLC profileof FIG. 1.

FIG. 2D represents the infra-red spectrum for Peak 6 of the GLC profileof FIG. 1.

FIG. 2E represents the infra-red spectrum for Peak 7 of the GLC profileof FIG. 1.

FIG. 2F represents the infra-red spectrum for Peak 8 of the GLC profileof FIG. 1.

FIG. 2G represents the infra-red spectrum for Peak 9 of the GLC profileof FIG. 1.

FIG. 2H represents the infra-red spectrum for Peak 10 of the GLC profileof FIG. 1.

FIG. 2J represents the NMR spectrum for a mixture of compounds havingthe structures: ##STR6## produced according to Example I.

FIG. 2K represents the NMR spectrum for the compound having thestructure: ##STR7## produced according to Example I.

FIG. 2L represents the NMR spectrum for the compound containing thestructure: ##STR8## produced according to Example I.

FIG. 3 represents the GLC profile for the reaction product of ExampleII, containing a mixture of compounds, each of which is definedaccording to the generic structure: ##STR9## wherein in each of themolecules, one of the dashed lines represents a carbon-carbon doublebond and each of the other of the dashed lines represent a carbon-carbonsingle bond.

FIG. 4 represents the infra-red spectrum for the reaction product ofExample II containing the compounds having the structures: ##STR10##

FIG. 5 represents the mass spectrum for the reaction product of ExampleII containing the compounds having the structures: ##STR11##

FIG. 6 represents the GLC profile for the reaction product of ExampleIIIA containing structures defined according to the genus having thestructure: ##STR12## wherein in each of the molecules of the mixture,one of the dashed lines represents a carbon-carbon double bond and eachof the other of the dashed lines represent carbon-carbon single bonds.

FIG. 7 represents the GLC profile for the reaction product of ExampleIIIB containing a mixture of compounds defined according to thestructure: ##STR13## wherein in each of the molecules of the mixture,one of the dashed lines represents a carbon-carbon double bond and eachof the other of the dashed lines represent carbon-carbon single bonds.

FIG. 8 represents the GLC profile for the reaction product of ExampleIVA containing a mixture of compounds defined according to the genushaving the structure: ##STR14## wherein in each of the molecules of themixture, one of the dashed lines represents a carbon-carbon double bondand each of the other of the dashed lines represents carbon-carbonsingle bonds.

FIG. 9 is the GLC profile for the reaction product mixture preparedaccording to Example V (conditions: S.F. 96 column, 6 foot×1/4 inch;programmed at 100°-220° C. at 8° C. per minute).

FIG. 10 is the infra red spectrum for the reaction product mixtureprepared according to Example V containing compounds defined accordingto the structure: ##STR15##

FIG. 11 is the GLC profile for fraction 4 of the distillation product ofthe reaction product of Example VI containing the compounds definedaccording to the structure: ##STR16##

FIG. 12 is the infra red spectrum for the reaction product of Example VIcontaining the compounds having the structure: ##STR17## wherein in eachof the compounds one of the dashed lines represents a carbon-carbondouble bond and each of the other of the compounds representcarbon-carbon single bonds.

FIG. 13 is the NMR spectrum for fraction 4 of the distillation productof the reaction product of Example IV containing the compounds definedaccording to the structure: ##STR18## wherein in each of the compoundsof the mixture one of the dashed lines represents a carbon-carbon doublebond and each of the other of the compounds represent carbon-carbonsingle bonds.

DISCLOSURES INCORPORATED BY REFERENCE HEREIN

The following applications for United States Letters Patent areincorporated by reference herein:

(a) U.S. Application for Letters Patent Ser. No. 160,788 filed on June19, 1980, now U.S. Pat. No. 4,287,084, (entitled: "Use of Mixture ofAliphatic C₁₀ Branched Olefins in Augmenting or Enhancing the Aroma ofPerfumes and/or Perfumed Articles") setting forth the use of thecompounds having the structures: ##STR19## or generically the compoundsdefined according to the structure: ##STR20## wherein R₁ ", R₂ ", R₃ ",R₄ " and R₅ " represents hydrogen or methyl with three of R₁ ", R₂ ", R₃", R₄ " and R₅ " representing methyl and the other two of R₁ ", R₂ ", R₃", R₄ " and R₅ " representing hydrogen;

(b) Application for U.S. Letters Patent Ser. No. 188,576 filed on Sept.18, 1980, now U.S. Pat. No. 4,303,555, a continuation-in-part of Ser.No. 160,788 filed on June 19, 1980; and

(c) Application for U.S. Letters Patent Ser. No. 184,132 filed on Sept.4, 1980, now U.S. Pat. No. 4,321,255, entitled "Branched Ketones,Organoleptic Uses Thereof and Process for Preparing Same" disclosing thereaction: ##STR21## wherein R₁ ', R₂ ' and R₃ ' represent C₁ -C₃ loweralkyl and R₄ ' is either of R₁ ', R₂ ' or R₃ ' and wherein X' is chloroor bromo, and the use of the resulting compounds for their organolepticproperties.

The instant application is directed to the use of the compounds definedaccording to the generic structure: ##STR22## as starting materialswherein R₄ ' is C₁ -C₃ lower alkyl and wherein one of the dashed linesrepresents a carbon-carbon double bond and each of the other of thedashed lines represent carbon-carbon single bonds produced according tothe process of Application for United States Letters Patent Ser. No.184,132 filed on Sept. 4, 1980 entitled "Branched Ketones, OrganolepticUses Thereof and Process for Preparing Same."

THE INVENTION

It has now been determined that certain branched chain olefinicsecondary alcohols are capable of imparting a variety of flavors andfragrances to various consumable materials. Briefly, our inventioncontemplates branched chain unsaturated secondary alcohols definedaccording to the generic structure: ##STR23## wherein R₁ representsmethyl or isopropyl alcohol and wherein the dashed lines represents acarbon-carbon double bond and each of the other of the dashed linesrepresent carbon-carbon single bonds.

The branched chain olefinic secondary alcohols of our invention areeither usable in admixture with one another, or the isomers are usablein admixture with one another such as mixtures of compounds definedaccording to the structure: ##STR24## wherein one of the dashed lines ineach of the molecules of the mixture represents a carbon-carbon doublebond and each of the other of the dashed lines of each of the moleculesof the mixture represent carbon-carbon single bonds or they may be usedas individual compounds which are, for example, defined according tostructures such as: ##STR25## (wherein R₁ is methyl or isopropyl and R₂is hydrogen) ##STR26## wherein the compound having the structure:##STR27## differs from the compound having the structure: ##STR28## andthat one is "cis" with respect to the methyl groups on the carbon atomswhich make up the carbon-carbon double bond and wherein the structure:##STR29## represents a "trans" isomer with respect to the methylmoieties bonded to the carbon atoms making up the carbon-carbon doublebond and wherein the structure: ##STR30## represents a stereo isomericconfiguration wherein the carbon atoms having the "*" are asymmetriccarbon atoms in the molecule and wherein the compound is a "trans"isomer with respect to the methyl moieties bonded to the carbon atomswhich make up the carbon-carbon double bond.

The branched chain olefinic secondary alcohols of our invention areobtained by means of reaction of the ketones produced according toapplication for U.S. Letters Patent 4,321,255 issued on Mar. 23, 1982entitled "BRANCHED KETONES, ORGANOLEPTIC USES THEREOF AND PROCESS FORPREPARING SAME" with a reducing agent such as:

(a) one or more alkali metal borohydrides, e.g. sodium borohydride,lithium borohydride and potassium borohydride;

(b) hydrogen, using a catalyst such as 5% palladium on carbon, 5%palladium on calcium carbonate or palladium on barium sulfate (e.g."Lindlar Catalyst"); or

(c) lithium aluminum hydride;

(d) aluminum alkoxides, such as aluminum isopropoxide and aluminumsecondary epoxide,

according to the reaction: ##STR31##

When carrying out the reaction for reacting the ketone having thestructure: ##STR32## with an alkali metal borohydride such as sodiumborohydride the reaction is carried out in the presence of a proticsolvent which reacts relatively slowly or not at all with the alkalimetal borohydride when compared to the reaction of the alkali metalborohydride with the ketone having the structure: ##STR33## Specificworkable solvents which must "solvate" the carbonyl moiety in order toenable the reaction to proceed at a reasonable rate are isopropylalcohol, n-propenol, n-butanol, isobutyl alcohol and t-butyl alcohol.

The temperature of reaction is necessarily a function of:

(i) the yield desired

(ii) the time of reaction

(iii) the nature of the solvent used

(iv) the pressure of the vapor over the reaction mass

(v) the concentration of the reactant, the alkali metal borohydride andthe ketone having the structure: ##STR34## in the solvent (vi) thedesired rate of reaction, and

(vii) the ratio of alkali metal borohydride:ketone having the structure:##STR35## It is preferred to carry out the reaction at reflux conditionsat atmospheric pressure. Thus, when using isopropyl alcohol as a solventwhere the mole ratio of alkali metal borohydride:ketone having thestructure: ##STR36## is 1:2, the temperature of reaction is about 73° C.and the time of reaction is 3 hours. In the case of using an alkalimetal borohydride, the alcohol acts as a "solvent" and not as a"reactant".

On the other hand, when using the aluminum alkoxide such as aluminumsecondary butoxide and aluminum isopropaxide, the solvent must be asource of hydrogen which is the actual reducing agent in the reaction.Thus, it is necessary that the "solvent" be a "reactable solvent" suchas isopropyl alcohol and not merely a solvating solvent.

The mole ratio of alkali metal borohydride:ketone having the structure:##STR37## is preferably 1:2, which means that the equivalent ratioregarding hydrogen:ketone is 2:1; that is, the alkali metal borohydrideis in 100% excess since theoretically only one mole of the alkali metalborohydride is needed to react with 4 moles of ketone, since one mole ofalkali metal borohydride provides 4 atoms of hydrogen. Interestingly andsurprisingly in this reaction and in all of the above reactions thedouble bond does get reduced during the reaction.

Insofar as the hydrogenation reaction is concerned with the ketonehaving the structure: ##STR38## as the starting material or one of theketones defined according to the structure: ##STR39## as being astarting material, the ketone is reacted with hydrogen in the presenceof a Raney nickel catalyst or a palladium on carbon catalyst or a"Lindlar" catalyst (palladium on calcium carbonate) or palladium onbarium sulface. The percentage of palladium in the palladium on carboncatalyst or in the palladium on calcium carbonate catalyst or in thepallaidum on barium sulfate catalyst varies from about 2% up to about 7%with a percentage of palladium in the palladium on carbon catalyst or inthe palladium on calcium carbonate catalyst or in the palladium onbarium sulfate catalyst being preferred to be 5%. The temperature ofreaction for the hydrogenation may vary from about 10° C. up to about100° C. with a preferred reaction temperature of 25° C.-35° C. Since thereaction is exothermic it is usually necessary to provide externalcooling to the reaction mass during the course of the reaction. Thepressure of hydrogen over the reaction mass may vary from about 5 psigup to about 100 psig with the most preferred pressure being 20 psig.Pressures greater than 150 psig will give rise to amounts of fullysaturated alcohol. The hydrogenation reaction may be carried out in thepresence of or in the absence of a solvent. When a solvent is used, itis required that it be an inert (non-reactive) solvent such as isopropylalcohol, hexane or ethanol. If a solvent is used it is preferred thatthe mole ratio of solvent:ketone having the structure: ##STR40## beapproximately 1:1. Whereas a palladium containing catalyst is used thepercentage of catalyst in the reaction mass may vary from 0.125% up toabout 2.0% with a percentage of catalyst of about 0.25% being preferred.Where a Raney nicket catalyst is used, the percentage of catalyst in thereaction mass may vary from about 3% up to about 10% with a percentageof catalyst of about 5% being preferred.

If the reaction is carried out in the presence of the alkali metalborohydride, the reaction mass is neutralized using weak acid and thereaction product is then further washed with water and if necessarysodium carbonate. In any event, the reaction mass is ultimatelydistilled fractionally to yield the desired saturated alcohol producthaving the generic structure: ##STR41## wherein R₁ is methyl orisopropyl and one of the dashed lines represents carbon-carbon doublebond and the other of the dashed lines represents carbon-carbon singlebonds.

Examples of branched chain unsaturated alcohols of my invention andtheir perfumery and tobacco flavor properties according to my inventionare as follows:

                  TABLE I                                                         ______________________________________                                                     Organoleptic Properties                                          Identification of                                                                            Perfumery    Tobacco                                           Secondary Alcohol                                                                            Properties   Properties                                        ______________________________________                                         ##STR42##     A woody, amber, fruity aroma with strong vetiver nuances                      on dry-out after six hours                                                                 An intense woody, oriental- like and minty                                    aroma and taste both prior to and on smoking                                  in the main- stream and the  sidestream           ponent of the mixture                                                         one of the dashed lines                                                       represents a carbon-                                                          carbon double bond and                                                        each of the other of                                                          the dashed lines repre-                                                       sents carbon-carbon                                                           single bonds, produced                                                        according to the process                                                      of Example V, infra.                                                          Mixture of compounds                                                                         An intense woody                                                                           An oriental                                       defined according to                                                                         aroma        woody aroma and                                   the structure:              taste both prior to                                ##STR43##                  and on smoking in the mainstream and in the                                   side- stream                                      wherein in each of the                                                        molecules of the mix-                                                         ture one of the dashed                                                        lines represents a                                                            carbon-carbon double                                                          bond and each of the                                                          other of the dashed                                                           lines represents                                                              carbon-carbon single                                                          bonds, prepared                                                               according to the                                                              process of Example                                                            VI, distillation                                                              fraction 4, infra.                                                            ______________________________________                                    

The individual branched chain secondary alcohols of our invention can beobtained in purer form or in substantially pure form by conventionalpurification techniques. Thus, the products can be purified bydistillation, extraction, crystallization, preparative chromatographictechniques (including high pressure liquid chromatography) and the like.It has been found desirable to purify the branched chain unsaturatedsecondary alcohols of our invention by fractional distillation undervacuum.

It will be appreciated from the present disclosure that the branchedchain secondary alcohols and mixtures thereof according to the presentinvention can be used to alter, vary, fortify, modify, enhance orotherwise improve the flavor and aroma of a wide variety of materialswhich are ingested, consumed or otherwise organoleptically sensed,particularly including perfume compositions, perfumed articles andsmoking tobacco compositions and smoking tobacco articles.

The term "alter" in its various forms will be understood herein to meanthe supplying or imparting of a flavor character or note or aromacharacter to an otherwise bland, relatively aromaless or tastelesssubstance, or augmenting an existing flavor or aroma characteristicwhere the natural flavor or aroma is deficient in some regard orsupplementing the existing flavor or aroma impression to modify theorganoleptic character.

The term "enhance" is intended herein to mean the intensification of aparticular aroma or taste nuance (particularly in perfumes, perfumedarticles or smoking tobaccos) without the changing of the quality ofsaid nuance and without adding an additional aroma or taste nuance tothe consumable material, the organoleptic properties of which areenhanced.

The term "tobacco" will be understood herein to mean a natural productsuch as, for example, burley, Turkish tobacco, Maryland tobacco,flue-cured tobacco and the like including tobacco-like or tobacco-basedproducts such as reconstitued or homogenized leaf and the like, as wellas tobacco substitutes intended to replace natural tobacco, such aslettuce and cabbage leaves and the like. The tobaccos and tobaccoproducts in which the branched chain unsaturated secondary alcohols ofmy invention are useful include those designed or used for smoking suchas in cigarette, cigar and pipe tobacco, as well as products such assnuff, chewing tobacco and the like.

The branched chain unsaturated secondary alcohols of my invention can beused to contribute warm, vetiver-like, woody, fruity and amber aromas.As olfactory agents the branched chain unsaturated secondary alcohols ofthis invention can be formulated into or used as components of a"perfume composition".

The term "perfume composition" is used herein to mean a mixture oforganic compounds, including, for example, alcohols, other than thealcohols of this invention, aldehydes, ketones, nitriles, esters, andfrequently hydrocarbons which are admixed so that the combined odors ofthe individual components produce a pleasant or desired fragrance. Suchperfume compositions usually contain: (a) the main note of the "bouquet"or foundation-stone of the composition; (b) modifiers which round offand accompany the main note; (c) fixatives which include odoroussubstances which lend a particular note to the perfume throughout allstages of evaporation, and substances which retard evaporation; and (d)topnotes which are usually low-boiling fresh-smelling materials.

In perfume compositions, the individual component will contribute itsparticular olfactory characteristics but the overall effect of theperfume composition will be the sum of the effect of each ingredient.Thus, the individual compounds of this invention, or mixtures thereof,can be used to alter the aroma characteristics of a perfume composition,for example, by highlighting or moderating the olfactory reactioncontributed by another ingredient in the composition.

The amount of branched chain unsaturated secondary alcohols of thisinvention which will be effective in perfume compositions depends on mayfactors, including the other ingredients, their amounts and the effectswhich are desired. It has been found that perfume compositionscontaining as little as 0.05% and as much as 5% of the branched chainunsaturated secondary alcohols of this invention can be used to impart,augment or enhance warm, intense, amber, woody, fruity and vetiver aromaprofiles to soaps, cosmetics, solid or liquid anionic, cationic,nonionic and zwitterionic detergents and other products. The amountemployed can range up to 50% of the fragrance and can be as low as 1% ofthe original fragrance and will depend on considerations of cost, natureof the end product, the effect desired in the finished product and theparticular fragrance sought.

The branched chain unsaturated secondary alcohols of this invention canbe used alone or in a perfume composition as an olfactory component indetergents, and soaps, space odorants and deodorants, perfumes,colognes, toilet waters, bath salts, hair preparations such as lacquers,brilliantines, pomades, and shampoos, cosmetic preparations such ascreams, deodorants, hand lotions and sun screens, powders such as talcs,dusting powders, face powder, and the like. When used as an olfactorycomponent of a perfumed article, as little as 0.05% of one or more ofthe branched chain unsaturated secondary alcohols will suffice to impartwarm, vetiver, woody, amber and fruity aroma nuances. Generally no morethan 5.0% is required.

In addition, the perfume composition can contain a vehicle or carrierfor the branched chain unsaturated secondary alcohols taken alone ortaken together with other ingredients. The vehicle can be a liquid suchas an alcohol such as ethanol, a glycol such as propylene glycol, or thelike. The carrier can be an absorbent solid such as a gum or amicroporous polymer or components for encapsulating the composition suchas by means of coacervation.

An additional aspect of our invention provides an organolepticallyimproved smoking tobacco product and additives therefor, as well asmethods of making the same which overcome specific problems heretoforeencountered in which specific desired oriental and woody and mintyflavor and aroma characteristics are created or enhanced and may bereadily controlled and maintained at the desired uniform levelregardless of variations in the tobacco components of the blend.

This invention further provides improved tobacco additives and methodswhereby various desirable woody, oriental and minty flavor and aromacharacteristics may be imparted to smoking tobacco products and may bereadily varied and controlled to produce the desired uniform flavoringcharacteristics prior to and on smoking in the mainstream and in thesidestream.

In carrying out this aspect of our invention, we add to smoking tobaccomaterials or a suitable substitute therefor (e.g. dried lettuce leaves)an aroma and flavor additive containing as an active ingredient at leastone of the secondary alcohols of my invention.

In addition to the one or more secondary alcohols of my invention, otherflavoring and aroma additives may be added to the smoking tobaccomaterial or substitute therefor either separately or in admixture withthe secondary alcohols as follows:

I. Synthetic Materials:

Beta-ethyl-cinnamaldehyde;

Eugenol;

Dipentene;

Damascone;

1-[3-(methylthio)butyro]2,3,3-trimethyl-cyclohexene;

Damascenone;

Maltol;

Ethyl maltol;

Delta undecalactone;

Delta decalactone;

Benzaldehyde;

Amyl acetate;

Ethyl butyrate;

Ethyl acetate;

2-Hexenol-1,2methyl-isopropyl-1,3-nonadiene-8-one;

2,6-Dimethyl-2,6-undecadiene-10-one;

2-Methyl-5-isopropyl acetophenone;

2-Hydroxy-2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)-decahydronaphthalene;

Dodecahydro-3a,6,6,9a-tetramethyl naphtho-(2-1-b)-furan;

4-Hydroxy hexanoic acid, gamma lactone;

Polyisoprenoid hydrocarbons defined in Example V of U.S. Pat. No.3,589,372, issued on June 29, 1971.

II. Natural Oils

Celery seed oil;

Coffee extract;

Bergamot Oil;

Cocoa extract;

Nutmeg oil; and

Origanum oil.

An aroma and flavoring concentrate containing one or more of thesecondary alcohols of my invention and if desired one or more of theabove indicated additional flavoring additives may be added to thesmoking tobacco material, to the filter or to the leaf or paper wrapper.The smoking tobacco material may be shredded, cured, cased and blendedtobacco material or reconstituted tobacco material or tobaccosubstitutes (e.g., lettuce leaves) or mixtures thereof. The proportionsof flavoring additives may be varied in accordance with taste butinsofar as the augmentation, or the enhancement or the imparting of thewoody, oriental and minty notes are concerned, we have found thatsatisfactory results are obtained if the proportion by weight of the sumtotal of secondary alcohols of my invention is between 250 ppm and 1,500ppm (0.025%-1.5%) of the active ingredients to the smoking tobaccomaterial. I have further found that satisfactory results are obtained ifthe proportion by weight of the sum total of secondary alcohols used toflavoring material is between 2,500 and 10,000 ppm (0.25%-1.5%).

Any convenient method for incorporating the secondary alcohols in thetobacco product may be employed. Thus, the secondary alcohols takenalone or along with other flavoring additives may be dissolved in asuitable solvent such as ethanol, n-pentane, diethyl ether and/or othervolatile organic solvents and the resulting solution may either besprayed on the cured, cased and blended tobacco material or the tobaccomaterial may be dipped into such solution. Under certain circumstances,a solution of one or more secondary alcohols of this invention takenalone or further together with other flavoring additives as said forthabove may be applied by means of a suitable applicator such as a brushor roller on the paper or leaf wrapper for the smoking product, or itmay be applied to the filter by either spraying or dipping or coating.

Furthermore, it will be apparent that only a portion of the tobacco orsubstitute therefor need be treated and the thus treated tobacco may beblended with other tobaccos before the ultimate tobacco product isformed. In such cases, the tobacco treated may have one or more of thesecondary alcohols of this invention in excess of the amounts orconcentrations above indicated so that when blended with other tobaccos,the final product will have the percentage within the indicated range.

In accordance with one specific example of my invention, an aged, curedand shredded domestic burley tobacco is spread with a 20% ethyl alcoholsolution of a mixture of compounds having the structure: ##STR44##produced according to Example V, infra, in an amount to provide atobacco composition containing 800 ppm by weight of the secondaryalcohol mixture on a dry basis. Thereafter, the ethyl alcohol is removedby evaporation and the tobacco is manufactured into cigarettes by theusual techniques. The cigarette when treated as indicated has a desiredand pleasing aroma which is detectable in the main and side streams whenthe cigarette is smoked. This aroma is described as being sweet,oriental-like, woody and turkish tobacco-like with intense mintynuances.

While our invention is particularly useful in the manufacture of smokingtobacco, such as cigarette tobacco, cigar tobacco and pipe tobacco,other tobacco products formed from sheeted tobacco dust or fines mayalso be used. Likewise, the secondary alcohols of my invention can beincorporated with materials such as filter tip materials, seam paste,packaging materials and the like which are used along with tobacco toform a product adapted for smoking. Furthermore, the secondary alcoholsof this invention can be added to certain tobacco substitutes of naturalor synthetic origin (e.g. dried lettuce leaves) and, accordingly, byterm "tobacco" as used throughout this specification is meant anycomposition intended for human consumption by smoking or otherwise,whether composed of tobacco plant parts or substitute materials or both.

The following examples A-IV are given to illustrate techniques forproducing the precursors for the compounds of my invention as it ispresently preferred to practice it. Example V and onwards are given toillustrate embodiments of my invention as it is presently preferred topractice it. It will be understood that these examples are illustrativeand the invention is not to be considered restricted thereto except asindicated in the appended claims.

EXAMPLE A PREPARATION OF DI-ISOAMYLENE DERIVATIVES

Reaction: ##STR45## (wherein in each of the molecules indicated, one ofthe dashed lines is a carbon-carbon double bond and the other of thedashed lines are carbon-carbon single bonds).

Di-isoamylene is prepared according to one of the procedures set forthin the following references:

i--Murphy & Lane, Ind. Eng. Chem., Prod. Res. Dev., Vol. 14, No. 3, 1975p. 167 (Title: Oligomerization of 2-Methyl-2-Butene in Sulfuric andSulfuric-Phosphoric Acid Mixtures).

ii--Whitmore & Mosher, Vol. 68, J. Am. Chem. Soc., February, 1946, p.281 (Title: The Depolymerization of 3,4,5,5-Tetramethyl-2-hexene and3,5,5-Trimethyl-2-heptene in Relation to the Dimerization ofIsoamylenes)

The resulting material was distilled in a fractionation column in orderto separate the di-isoamylene from the higher molecular weight polymers,which are formed during the reaction as by-products.

FIG. AA represents the GLC profile for the reaction product of Example Ausing a 70% sulfuric acid catalyst at 35% C.

FIG. AB represents the GLC profile for the reaction product of Example Ausing an Amberlyst® 15 acidic ion exchange resin catalyst at atemperature of 150° C.

FIG. AC represents the GLC profile for the reaction product of ExampleA, using an Amberlyst® 15 catalyst at 100° C.

FIG. AD represents and GLC profile for the reaction product of ExampleA, using a sulfuric acid catalyst and an alpha-methylstyrene diluent at35° C. according to the conditions of U.K. Pat. No. 796,130 (crudereaction product).

FIG. AE represents the GLC profile for the reaction product of ExampleA, using a sulfuric acid catalyst, at 35° C. and an alpha-methyl styrenediluent according to the conditions of U.K. Pat. No. 796,130 (distilledreaction product).

FIG. BA represents the NMR spectrum for Peak 1 of the GLC profile ofFIG. AE.

FIG. BB represents the infra-red spectrum for Peak 1 of the GLC profileof FIG. AE.

FIG. CA represents the MNR spectrum for Peak 2 of the GLC profile ofFIG. AE.

FIG. CB represents the infra-red spectrum for Peak 2 of the GLC profileof FIG. AE.

FIG. D represents the MNR spectrum for Peak 2 of the GLC profile of FIG.AB.

EXAMPLE I PREPARATION OF ACETYL DERIVATIVE OF DIISOAMYLENE

Reaction: ##STR46## wherein in each of the structures containing dashedlines, these structures represent mixtures of molecules wherein in eachof the molecules, one of the dashed lines represents a carbon-carbondouble bond and each of the other of the dashed lines respresentcarbon-carbon single bonds.

Into a 2-liter reaction flask equipped with stirrer, thermometer, reflexcondenser and heating mantle, is placed 1000 g of acetic anhydride and80 g of boron trifluoride diethyl etherate. The resulting mixture isheated to 80° C. and, over a period of 40 minutes, 690 g of diisoamyleneprepared according to the illustration in Example A, supra is added. Thereaction mass is maintained at 82°-85° C. for a period of 5.5 hours,whereupon it is cooled to room temperature. The reaction mass is thenadded to one liter of water and the resulting mixture is stirred therebyyielding two phases; an organic phase and an aqueous phase. The organicphase is separated from the aqueous phase and neutralized with twoliters of 12.5% sodium hydroxide followed by one liter of saturatedsodium chloride solution. The resulting organic phase is then dried overanhydrous sodium sulfate and distilled in a one plate distillationcolumn, yielding the following fractions:

    ______________________________________                                                  Vapor   Liquid           Weight of                                  Fraction  Temp.   Temp.     mm/Hg  Fraction                                   No.       (°C.)                                                                          (°C.)                                                                            Pressure                                                                             (g.)                                       ______________________________________                                        1         33/68   62/77     8/8    161                                        2         69      79        4      100                                        3         72      86        3.0    191                                        4         88      134       3.0    189                                        ______________________________________                                    

The resulting material is then distilled on a multi-plate fractionationcolumn, yielding the following fractions at the following reflux ratios:

    ______________________________________                                                Vapor   Liquid          Reflux Weight of                              Fraction                                                                              Temp.   Temp.    mm/Hg  Ratio  Fraction                               No.     (°C.)                                                                          (°C.)                                                                           Pressure                                                                             R/D    (g.)                                   ______________________________________                                        1       30/65   62/83    5/5    9:1    30.8                                   2       68      84       5      9:1    52.8                                   3       68      85       5      9:1    34                                     4       69      87       5      9:1    43                                     5       69      87       5      9:1    34                                     6       71      88       4      4:1    41                                     7       70      88       5      4:1    36.5                                   8       71      91       5      4:1    42                                     9       73      95       3      4:1    42.5                                   10      80      106      3      4:1    39                                     11      80      142      3      4:1    50.8                                   12      80      220      3      4:1    24                                     ______________________________________                                    

GLC, NMR, IR and mass spectral analyses yield the information that theresulting material is a mixture of cis and trans isomers having ageneric structure: ##STR47## wherein in each of the molecules, one ofthe dashed lines is a carbon-carbon double bond and the other of thedashed lines is a carbon-carbon single bond and, primarily, this mixturecontains the molecular species (cis and trans isomers) as follows:##STR48##

FIG. 1 sets forth the GLC profile for the reaction product of Example I,containing compounds defined according to the structure: ##STR49##wherein in each molecule of the mixture, one of the dashed lines is acarbon-carbon double bond and the other of the dashed lines arecarbon-carbon single bonds.

FIG. 2A represents the infra-red spectrum of Peak 3 of the GLC profileof FIG. 1.

FIG. 2B represents the infra-red spectrum of Peak 4 of the GLC profileof FIG. 1.

FIG. 2C represents the infra-red spectrum for Peak 5 of the GLC profileof FIG. 1.

FIG. 2D represents the infra-red spectrum for Peak 7 of the GLC profileof FIG. 1.

FIG. 2E represents the infra-red spectrum for Peak 7 of the GLC profileof FIG. 1.

FIG. 2F represents the infra-red spectrum for Peak 8 of the GLC profileof FIG. 1.

FIG. 2G represents the infra-red spectrum for Peak 9 of the GLC profileof FIG. 1.

FIG. 2H represents the infra-red sprectrum for peak "10" of the GLCprofile of FIG. 1.

FIG. 2J represents the NMR spectrum for a mixture of compounds havingthe structures: ##STR50## produced according to Example I.

FIG. 2K represents the NMR spectrum for the compound having thestructure: ##STR51## produced according to Example I.

FIG. 2L represents the NMR spectrum for the compound containing thestructure: ##STR52## produced according to Example I.

EXAMPLE II PREPARATION OF ISOBUTYRYL DERIVATIVE OF DIISOAMYLENE

Reaction: ##STR53## wherein in each of the structures containing dashedlines, these structures represent mixtures of molecules wherein in eachof the molecules, one of the dashed lines represents a carbon-carbondouble bond and each of the other of the dashed lines representcarbon-carbon single bonds.

Into a 5-liter reaction flask, equipped with reflux condenser, additionfunnel, thermometer, Thermowatch, heating mantle and nitrogen purgeaccessory is placed 1361 g (8.6 moles) of isobutyric anhydride. 105 ml(0.86 moles) of boron trifluoride etherate is then added to theisobutyric anhydride. The resulting mixture is then heated to 65° C.Over a period of 4 hours, 1725 g (8.6 moles) of diisoamylene preparedaccording to the illustration of Example A is added to the reactionmass, while maintaining the reaction mass at a temperature of 83°-85° C.

The reaction mass is then cooled to room temperature and is added to a5-liter separatory funnel. 75 ml of 50% sodium hydroxide (aqueous) and100 ml water is then added to the reaction mass thus yielding twophases, an aqueous phase and an organic phase. The lower aqueous phaseis removed and the organic phase is washed as follows:

A--1 liter saturated sodium chloride

B--1 liter 5% aqueous sodium hydroxide

C--1 liter saturated sodium chloride

D--1 liter 12.5% sodium hydroxide

E--1 liter 12.5% sodium hydroxide

The reaction mass is then distilled on a two inch splash column packedwith stones yielding the following fractions:

    ______________________________________                                               Vapor   Liquid            Weight of                                    Fraction                                                                             Temp.   Temp.      mm/Hg  Fraction                                     No.    (°C.)                                                                          (°C.)                                                                             Pressure                                                                             (g.)                                         ______________________________________                                        1      29/54   54/68      29/24  Starting Material                            2      51      68         14     "                                            3      90      68         11     "                                            4      64      98         11     "                                            5      92/94   102/108    7/5    378                                          6      135     165         5     257                                          ______________________________________                                    

Fractions 5 and 6 of the resulting distillate are then bulked andredistilled yielding the following fractions:

    ______________________________________                                               Vapor    Liquid          Reflux Weight of                              Fraction                                                                             Temp.    Temp.    mm/Hg  Ratio  Fraction                               No.    (°C.)                                                                           (°C.)                                                                           Pressure                                                                             R/D    (g.)                                   ______________________________________                                        1      15/45    88/92    3/2.5  4:1    21                                     2      60        99      2.4    4:1    13                                     3      67        98      2.4    4:1    35                                     4      69        97      2.2    4:1    49                                     5      70        99      2.2    4:1    59                                     6      70       101      2.2    4:1    50                                     7      70       101      2.0    4:1    37                                     8      84       112      1.7    4:1    33                                     9      84       112      1.7    4:1    63                                     10     78       119      1.8    4:1    37                                     11     84       122      1.7    4:1    51                                     12     92       121      1.7    4:1    43                                     13     101      156      1.6    4:1    27                                     14     121      178      1.6    4:1    85                                     15     110      220      1.6    4:1    33                                     ______________________________________                                    

Fractions 3-9 of this distillation are then rebulked and redistilled ona 12 inch Goodloe Silver Mirror column yielding the following fractions:

    ______________________________________                                               Vapor    Liquid          Reflux                                                                              Weight of                               Fraction                                                                             Temp.    Temp.   mm/Hg   Ratio Fraction                                No.    (°C.)                                                                           (°C.)                                                                          Pressure                                                                              R/D   (g.)                                    ______________________________________                                        1      47/60    84/92   1.6/1.2 4:1                                           2      67       93      1.2     4:1   50                                      3      67       94      1.2     4:1   50                                      4      67       95      1.2     4:1   52                                      5      67       95      1.2     4:1   50                                      6      67       98      1.2     4:1   57                                      7      67       101     1.2     4:1   57                                      8      72       212     1.2     4:1   42                                      ______________________________________                                    

The resulting reaction product is analyzed by means of GLC, NMR, IR andmass spectral analyses and this confirms that the reaction product is amixture of compounds defined according to the generic structure:##STR54## wherein in each of the molecules, one of the dashed lines is acarbon-carbon double bond and the other two of the dashed linesrepresent carbon-carbon single bonds. The major components of thismixture are compounds having the structures: ##STR55##

FIG. 3 represents the GLC profile for the reaction product of ExampleII, containing a mixture of compounds, each of which is definedaccording to the generic structure: ##STR56## wherein in each of themolecules, one of the dashed lines represents a carbon-carbon doublebond and each of the other of the dashed lines represent carbon-carbonsingle bonds.

FIG. 4 represents the infra-red spectrum for the reaction product ofExample II containing the compounds having the structures: ##STR57##

FIG. 5 represents the mass spectrum for the reaction product of ExampleII containing the compounds having the structures: ##STR58##

EXAMPLE III PREPARATION OF ACETYL DERIVATIVE OF DIISOAMYLENE

Reaction: ##STR59##

EXAMPLE IIIA

Into a 5-liter reaction flask equipped with electric stirrer,thermometer, addition funnel, 24/42 y-tube, condenser, heating mantleand nitrogen purge accessories are added 41 ml of 70% methane sulfonicacid followed by 30 g of phosphorous pentoxide. The resulting mixtureexotherms to 60° C.

Over a period of 7 minutes, 235 ml acetic anhydride is added to thereaction mass while maintaining same at a temperature of 65° C. Over aperiod of 30 minutes while maintaining the reaction temperature at 80°C., 516 ml of diisoamylene prepared according to the illustration ofExample A is added dropwise to the reaction mass. At the end of theaddition of the diisoamylene, GLC analysis indicates 42% product.

The reaction mass is added to a 5 gallon open head separatory flaskcontaining 1 liter of water.

The resulting mixture is washed with 1 liter of 12% sodium hydroxidefollowed by 1 liter of saturated sodium chloride solution. 100 mltoluene is added to help separation.

GLC, NMR, IR and mass spectral analyses yield the information that theresulting organic phase is a mixture of compounds defined according tothe generic structure: ##STR60## wherein in each of the molecules one ofthe dashed lines is a carbon-carbon double bond and the other two of thedashed lines represent carbon-carbon single bonds.

The resulting reaction product is then dried over anhydrous magnesiumsulfate and distilled on a 3-inch stone column yielding the followingfractions:

    ______________________________________                                                  Vapor        Liquid                                                 Fraction  Temp.        Temp.   mm/Hg                                          No.       (°C.) (°C.)                                                                          Pressure                                       ______________________________________                                        1         65/65        103/92  113/35                                         2         60            80     1                                              3         52            89     1                                              4         61           134     1                                              5         73           140     1                                              ______________________________________                                    

Fraction 2, 3 and 4 are bulked and evaluated for their organolepticproperties.

FIG. 6 represents the GLC profile for the reaction product of ExampleIIIA containing structures defined according to the genus having thestructure: ##STR61## wherein in each of the molecules of the mixture,one of the dashed lines represents a carbon-carbon double bond and eachof the other of the dashed lines represent carbon-carbon single bonds.

To a 500 ml reaction flask equipped with reflux condenser, additionfunnel, thermometer, Thermowatch, heating mantle, cooling bath andnitrogne purge accessories, is added 406 ml of acetic anhydride and 30ml boron trifluoride etherate. The reaction mass is heated to 60° C. andwhile maintaining the reaction mass at 60° over a period of 30 minutes,diisoamylene, prepared according to the illustration of Example A isadded. The resulting reaction mass is then heated, with stirring at 60°C. for a period of 12 hours. At the end of the 12 hour period, thereaction mass is distilled yielding the following fractions:

    ______________________________________                                                  Vapor   Liquid           Weight of                                  Fraction  Temp.   Temp.     mm/Hg  Fraction                                   No.       (°C.)                                                                          (°C.)                                                                            pressure                                                                             (g.)                                       ______________________________________                                        1         50/58   60/70     2.5    330                                        2         67      87        1.4    329                                        3         71      88        3.0     65                                        4         90      115       3.0    195                                        ______________________________________                                    

The resulting mass, by GLC, IR, NMR and mass spectral analyses consistof compounds defined according to the generic structure: ##STR62##wherein in each of the molecules one of the dashed lines is acarbon-carbon double bond and the other two of the dashed linesrepresent carbon-carbon single bonds.

FIG. 7 sets forth the GLC profile for the reaction product of thisExample IIIB.

EXAMPLE IV PREPARATION OF ISOBUTYRO DERIVATIVE OF DIISOAMYLENE

Reaction: ##STR63## wherein in each of the structure containing dashedlines, these structures represent mixtures of molecules wherein in eachof the molecules, one of the dashed lines represents a carbon-carbondouble bond and each of the other of the dashed lines representcarbon-carbon single bonds.

Into a 5000 ml reaction flask equipped with reflux condenser, additionfunnel, thermometer, Thermowatch, heating mantle, cooling bath andnitrogen gas purge accessory, is added 953 ml (6.0 moles) of isobutryicanhydride; 183 g of polyphosphoric acid and 135 ml 70% methane sulfonicacid. The reaction mass exotherms to 65° C.

Over a period of 20 minutes, while maintaining the reaction mass at 65°C. 1725 g (8.6 moles) of diisoamylene prepared according to theillustration of Example A is added to the reaction mass. The reactionmass is then heated to 85° C. and maintained at that temperature for aperiod of 10 hours. At the end of the 10 hour period, the reaction massis cooled and 100 g of sodium acetate and 1 liter of water are addedthereto. The resulting mixture is added to a 5 liter separatory funneland the organic layer is then washed as follows:

A--1 liter 12.5% sodium hydroxide

B--2 liter 12.5% sodium hydroxide

C--1 liter of saturated sodium chloride

The reaction mass is then distilled on a 1 foot Goodloe column yieldingthe following fractions:

    ______________________________________                                               Vapor    Liquid           Reflux                                                                              Weight of                              Fraction                                                                             Temp.    Temp.   mm/Hg    Ratio Fraction                               No.    (°C.)                                                                           (°C.)                                                                          Pressure R/D   (g.)                                   ______________________________________                                        1      35/50    88/93   1.8/0.8  4:1   41                                     2      63       100     .8       4:1   48                                     3      63       105     .6       4:1   73                                     4      66       114     .6       4:1   44                                     5      100      145     .6       4:1   42                                     6      101      225     .6       4:1   29                                     ______________________________________                                    

GLC, NMR, IR and mass spectral analyses confirm the information that theresulting product is a mixture of compounds defined according to thegeneric structure: ##STR64## wherein in each molecule of the mixture,one of the dashed lines is a carbon-carbon double bond and the other twoof the dashed lines represent carbon-carbon single bonds.

FIG. 8 sets forth the GLC profile for the reaction product of thisExample (Conditions: SF 96 column, six foot×1/4 inch; operated at 180°C. isothermal).

EXAMPLE V PREPARATION OF DIISOAMYLENE METHYL CARBINOL

Reaction: ##STR65##

Into a 2 liter reaction flask equipped with reflux condenser, additionfunnel, thermometer, heating mantle, and nitrogen bleed is placed 1liter of isopropyl alcohol followed by 38 grams of sodium borohydride.The resulting mixture is heated to reflux and over a period of 40minutes while maintaining the reflux temperature at 48° C. dropwiseaddition of acetyl diisoamylene prepared according to Example III (368grams) (bulked fractions 2-12 of the distillation) is carried out.

At the end of the addition of the 368 grams of acetyl diisoamylene, thereaction mass is stirred at a temperature of 73° C. for a period of 3hours. The reaction mass is then transferred to a separatory flaskcontaining 1 liter of water. 200 ml 5% hydrochloric acid is added to theseparatory funnel and the organic layer is separated from the inorganiclayer.

The organic layer is washed with one liter of sodium carbonate and isthen distilled on a 1" packed stone column yielding the followingfractions:

    ______________________________________                                                 Vapor         Liquid                                                 Fraction Temp.         Temp.   Pressure                                       Number   (°C.)  (°C.)                                                                          mm/Hg                                          ______________________________________                                        1        25/20         18/20   10                                             2        80            90      .2                                             3        81            92      .2                                             4        83            96      .2                                             5        81            130     .2                                             6        80            200     .2                                             ______________________________________                                    

The resulting product (bulked fractions 2-4) is analyzed by GLC, NMR andIR analysis to contain a mixture of compounds defined according to thestructure: ##STR66## wherein in each of the compounds one of the dashedlines represents a carbon-carbon double bond and each of the other ofthe dashed lines represent carbon-carbon single bonds.

Fractions 2-6 have long lasting woody, amber, slightly fruity aroma andon dry-out have long-lasting vetiver nuances.

FIG. 9 is the GLC profile of the reaction product (conditions: 60'×1/4"SF-96 column programmed at 100°-120° C. at 8° C. per minute).

FIG. 10 is the infra red spectrum for the distillation product, bulkedfractions 2-4.

EXAMPLE VI PREPARATION OF DIISOAMYLENE ISOPROPYL CARBINOL

Reaction ##STR67##

Into a 500 ml reaction flask equipped with reflux condenser, additionfunnel, heating mantle, thermometer and nitrogen blanket provision isplaced 210 grams of isobutyro diisoamylene prepared according to ExampleIV (bulked fractions 2-6). 18.7 grams of sodium borohydride is thendissolved in 100 ml ethanol. The resulting borohydride solution is thenadded to the isobutyro diisoamylene via the addition funnel whilerefluxing the reaction mass at 78°-80° C. over a 10 minute period. Afteraddition of the sodium borohydride, the temperature of reaction mass is80° C. The addition takes 10 minutes. The reaction mass is then heatedat 65°-78° C. for an additional 12 hours after which period of time thereaction mass is transferred to a separatory funnel containing one literof water. The organic phase is separated from the inorganic phase andthe organic phase is washed with two additional one liter portions ofwater and is then distilled on a micro-vigreux column yielding thefollowing fractions:

    ______________________________________                                                 Vapor         Liquid                                                 Fraction Temp.         Temp.   Pressure                                       Number   (°C.)  (°C.)                                                                          mm/Hg                                          ______________________________________                                        1        87/89         93/90   3/3                                            2        89            91      3                                              3        79            88      2.5                                            4        80            83      2                                              5        85            91      2                                              6        97            115     2                                              7        165           200     2                                              ______________________________________                                    

The resulting product has an intense, woody perfume aroma and a pleasantoriental/woody aroma in smoking tobacco both prior to and on smoking inthe main stream and in the side stream.

FIG. 11 is the GLC profile for fraction 4 of the distillation product ofthe reaction product.

FIG. 12 is the infra red spectrum for the aforementioned reactionproduct subsequent to distillation (fraction 4).

FIG. 13 is the NMR spectrum for the aforementioned fraction 4 of thedistillation product of the reaction product subsequent to distillation.

EXAMPLE VII PERFUME FORMULATION

The following vetiver perfume formulation is prepared:

    ______________________________________                                        Ingredients          Parts by Weight                                          ______________________________________                                        Vetivone             25                                                       Mixture of compounds defined                                                  according to the structure:                                                    ##STR68##                                                                    Prepared according to                                                         Example VI, fraction 4.                                                                            12                                                       Mixture of compounds defined                                                  according to the structure:                                                    ##STR69##                                                                    Prepared according to                                                         Example V, bulked fractions 2-4.                                                                   12                                                       Vetiverol            5                                                        Musk ketone          8                                                        Styrax essence       12.5                                                     ______________________________________                                    

The addition of the mixture of secondary alcohols prepared according toExamples V and VI impart to this vetiver formulation intense woody,long-lasting aromas with fruity and powerful amber nuances.

EXAMPLE VIII PERFUMED LIQUID DETERGENT

Concentrated liquid detergents with aromas as described in Table IIbelow (which detergents are produced from the lysine salt of n-dodecylbenzene sulfonic acid as more specifically described in U.S. Pat. No.3,948,818 issued on Apr. 6, 1976) are prepared containing one of thesubstances set forth in Table II below. They are prepared by adding andhomogeneously mixing the appropriate quantity of substance as indicatedin Table II below. The detergents all possess aroma profiles as setforth in Table II below, the intensity increasing with greaterconcentrations of the composition of matter as set forth in Table IIbelow:

                  TABLE II                                                        ______________________________________                                        Aroma Ingredient  Aroma Profile                                               ______________________________________                                        Secondary alcohol mixture                                                                       A fruity, amber, woody aroma                                defined according to the                                                                        with vetiver notes and having                               structure:        an intense vetiver aroma on                                                   dry-out.                                                     ##STR70##                                                                    wherein one of the dashed                                                     lines represents a carbon-                                                    carbon double bond and each                                                   of the other of the dashed                                                    lines represents carbon-                                                      carbon single bonds, prepared                                                 according to Example V,                                                       fractions 2-4.                                                                Mixture of compounds defined                                                                    An intense woody, long-                                     according to the structure:                                                                     lasting aroma with strong                                                     long-lasting vetiver                                         ##STR71##        nuances.                                                    produced according to Example                                                 VI, fraction 4, wherein in each of                                            the molecules of the mixture, one                                             of the dashed lines represents a                                              carbon-carbon double bond and                                                 each of the other of the dashed                                               lines represent carbon-carbon                                                 single bonds.                                                                 Perfume composition of                                                                          An intense vetiver aroma                                    Example VIII.     which is long-lasting                                                         containing woody, fruity                                                      and unusually powerful                                                        amber nuances.                                              ______________________________________                                    

EXAMPLE IX PREPARATION OF A COLOGNE AND HANDKERCHIEF PERFUME

Aroma imparting and augmenting ingredients as defined according to TableII in Example VIII are incorporated into colognes at concentrations of1.5%, 2.0%, 2.5%, 3.0%, 4.0% and 5.0% in 75%, 80%, 80%, 90% and 95%solutions of aqueous ethanol; and into handkerchief perfumes atconcentrations of 15%, 20%, 25% and 30% (in 80%, 85% and 95% aqueousethanol solutions). The use of the compositions of matter as set forthin Table II of Example VIII affords distinct and definitive aromaprofiles as set forth in Table II of Example VIII to the handkerchiefperfumes and to the colognes.

EXAMPLE X PREPARATION OF A SOAP COMPOSITION

One hundred grams of soap chips (IVORY®) manufactured by the Procter &Gamble Company of Cincinnati, Ohio, are melted and intimately admixedwith one of the aroma materials as set forth in Table II of Example VIIIsupra, the amount of composition of matter of Table II of Example VIIIbeing one gram of each composition of matter. The conditions of mixingare: 180° C., 3 hours, 12 atmospheres pressure. At the end of the mixingcycle, while the soap is still under 12 atmospheres pressure, themixture of soap and perfume ingredient is cooled to room temperature. Atthis temperature, the resulting mixture is in a solid stage. Theresulting soap block is then cut up into soap cakes. Each of the soapcakes manifests an excellent aroma as set forth in Table II of ExampleVIII. None of the soap samples show any discoloration even after twoweeks in the oven at 90 F.

EXAMPLE XI PREPARATION OF A DETERGENT COMPOSITION

A total of 100 grams of a detergent powder (nonionic detergent powdercontaining a proteolytic enzyme prepared according to Example I ofCanadian Pat. No. 985,190 issued on Mar. 9, 1976) is mixed with 0.15grams of one of the compositions of matter as set forth in Table II ofExample VIII until a substantially homogeneous composition is obtained.Each of the compositions has excellent aroma profiles as set forth inTable II of Example VIII.

EXAMPLE XII PERFUMED LIQUID DETERGENTS

Concentrated liquid detergents with rich, pleasant aromas as set forthin Table II of Example VIII are prepared containing 0.01%, 0.15% and0.02% of each of the compositions of matter set forth in Table II ofExample VIII. They are prepared by adding and homogeneously admixing theappropriate quantity of composition of matter of Table II of ExampleVIII in the liquid detergent. The liquid detergents are all producedusing anionic detergents containing a 50:50 mixture of sodium lauroylsarcosinate and potassium N-methyl lauroyl tauride. The detergents allpossess pleasant aromas as defined in Table II of Example VIII, theintensity increasing with greater concentrations of compositions ofmatter of Table II of Example VIII.

EXAMPLE XIII TOBACCO FORMULATION

A tobacco mixture is prepared by admixing the following ingredients:

    ______________________________________                                        Ingredients     Parts by Weight                                               ______________________________________                                        Bright          40.1                                                          Burley          24.9                                                          Maryland        1.1                                                           Turkish         11.6                                                          Stem (flue-cured)                                                                             14.2                                                          Glycerine       2.8                                                           Water           5.3                                                           ______________________________________                                    

Cigarettes are prepared from this tobacco.

The following flavor formulation is prepared:

    ______________________________________                                        Ingredients    Parts by Weight                                                ______________________________________                                        Ethyl butyrate .05                                                            Ethyl valerate .05                                                            Maltol         2.00                                                           Cocoa extract  26.00                                                          Coffee extract 10.00                                                          Ethyl alcohol  20.00                                                          Water          41.90                                                          ______________________________________                                    

The above stated tobacco flavor formulation is applied at the rate of1.0% to all of the cigarettes produced using the above tobaccoformulation. One-third of the cigarettes are then treated with 500 or1000 ppm of the secondary alcohol mixture defined according to thestructure: ##STR72## wherein in each of the molecules of the mixture,one of the dashed lines represents a carbon-carbon double bond and eachof the other of the dashed lines represent carbon-carbon single bonds.Another third of the cigarettes are treated with 500 or 1000 ppm of themixture produced according to Example VI defined according to thestructure: ##STR73## wherein in each of the molecules of the mixture,one of the dashed lines represents a carbon-carbon double bond and eachof the other of the dashed lines represent carbon-carbon single bonds.The last third of the cigarettes are "control cigarettes" and do notcontain any of the unsaturated alcohols of either Example V or ExampleVI but only contain untreated flavor formulation as set forth above. Thecontrol cigarettes and the treated experimental cigarettes are thenevaluated by paired comparison and the results are as follows:

The experimental cigarettes are found to have more body and to be, onsmoking, more Turkish tobacco-like, more aromatic and to have sweet,spicy, woody/oriental, minty and fruity aroma nuances in both the mainstream and the side stream with additional clovelike nuances withrespect to the composition of matter produced according to Example V.These aroma nuances are missing from the control cigarettes. Theexperimental cigarettes containing the composition of matter preparedaccording to Example V in the filter have a woody, tobacco characterwith heavy air-cured and cigar-like aroma nuances. The cigarettescontaining the composition of matter of Example VI in the filter havesweet, minty aroma nuances both prior to and on smoking. The descriptioncan also be set forth as "menthol-like".

What is claimed is:
 1. At least one compound defined according to thestructure: ##STR74## wherein R₁ is selected from the group consisting ofmethyl and isopropyl and wherein one of the dashed lines represents acarbon-carbon double bond and each of the other of the dashed linesrepresent carbon-carbon single bond.
 2. The compound of claim 1 whereinR₁ is methyl.
 3. The compound of claim 1 wherein R₁ is isopropyl.
 4. Acomposition of matter including a major proportion of a mixture ofcompounds defined according to the structure: ##STR75## wherein R₁represents methyl or isopropyl and in each of the molecules of themixture, one of the dashed lines represents a carbon-carbon double bondand each of the other of the dashed lines represent carbon-carbon singlebonds produced according to the process comprising the step ofintimately admixing a ketone having the structure: ##STR76## with areducing agent selected from the group consisting of (i) an alkali metalborohydride; (ii) lithium aluminum hydride and (iii) aluminumisopropylate and then fractionally distilling the resulting reactionmixture.
 5. The product of claim 4 wherein in the process the reducingagent is sodium borohydride and the process is carried out in thepresence of a protic solvent and the protic solvent is isopropylalcohol.
 6. The product of claim 4 wherein in the process for producingsaid product the reducing agent is sodium borohydride and the proticsolvent is isopropyl alcohol and the mole ratio of sodiumborohydride:ketone reactant having the structure: ##STR77## is about1:2.